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Jou al of Materials Chemistry A
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DOI: 10.1039/C5TA06548H
Journal Name
ARTICLE
followed by NaH (0.3 g, 12.5 mmol). This reaction mass was This above salt 4 (0.8 g, 1.35 mmol) was dissolved in ethanol
refluxed for 3h, cooled and added in ice cold water to give light along with terphthaldehyde (0.81 g, 1.35 mmol) and was
yellow color solid material and filtered. Product was further stirred at 5◦C followed by sodium ethoxide solution using Na
purified by column chromatography on a silica gel column metal (0.3 g, 13.04 mmol) and ethanol (4.94 mL) and stirred
using hexane and ethyl acetate as eluent [9:1 by vol.], to give for 2 h. This reaction mass was poured in cold water followed
1
white yellow product (2.88 gm, 96%), H NMR (400 MHz, CD
3
by extraction using chloroform. Solvent was removed under
COCD
m, 2H), 4.45(t, J =6.8 Hz ), 7.2 (m, 2H), 7.35-7.65 (m, 4H), 8.1- catalytic amount of iodine. This was refluxed for 8 h. in dark
.2 (d, J = 8.8, 2H). Elemental analysis calcd. for C18 21N, C and poured into cold solution of 0.1N NaOH followed by
86.05), H (8.47), N (5.55); found C (86.01), H (8.44), N (5.57).
-Hexyl-3-formyle carbazole (2)
3
): δ= 0.85 (m, J = 6.8 Hz, 3H), 1.15-1.5 (m, 6H), 1.8-1.9 vacuum and residues were dissolved in THF in presence of
3
4
(
8
H
(
extraction using dichloromethane. Solvent was removed under
vacuum and residues were purified by column
9
chromatography using hexane and ethyl acetate (1:1 by vol.),
1
0.247 g, 49%). H NMR (400 MHz, CDCl
The above compound 1 (1.5 g, 5.96 mmol) was subjected to
Vilsmeier-Hack procedure using POCl (0.55 mL, 6.16
(
3
): δ 0.9 (t, J = 6.8 Hz,
3
3
7
7
1
H), 1.35 (m, 6H), 1.6 (s, 1H), 1.9 (2H, m), 4.36 (d, J = 6 Hz, 2H),
mmol)/DMF (0.47 mL, 6.16 mmol) for formylation. After
formylation light yellow oily product was obtained. The
products were extracted with chloroform and purified by
column chromatography on a silica gel column using
petroleum ether and dichloromethane as eluent [4:1 by
.2 (d, J = 16 Hz, 1H), 7.35 (d, J = 7.6 Hz 1H), 7.35-7.5 (m, 4H),
.65 ( m, 2H), 7.85 (d, 1H), 8.19 (d, J = 6.8 Hz, 1H), 8.25 (s, 1H),
0.0 (s, 1H). Elemental analysis calcd. for C27H27NO, C (85.04),
H (7.10), N (3.66), O (4.19); found C (85.01), H (7.11), N (3.66),
O (4.19).
1
vol.],to give a faint yellow solid product (1.45 g, 87%). H NMR
(
400 MHz, CD
3
COCD
H), 2.0 (m, 2H), 4.55 (t, J = 4.0 Hz, 2H), 7.35-7.55 (m, 2H), 7.6-
.8 (dd, J = 8.0 Hz, 2H,), 8.0 (m,1H), 8.3 (m, 1H), 8.75 (m, 1H),
0.1 (s, 1H). Elemental analysis calcd. for C19 21NO, C (81.66),
3
): δ = 0.85 (t, J = 7.2 Hz, 3H), 1.2-1.5 (m,
2
-(-5-(4-(-2-(9-hexyl-9H-carbazol-3-yl)vinyl)benzylidene)-4-oxo-2-
6
7
1
thioxothiazolidin-3-yl)acetic acid (SK2) and 2-cyano-3-(4-((E)-2-(9-
hexyl-9H-carbazol-3-yl)vinyl)phenyl)acrylic acid (SK3)
H
H (7.61), N (5.04), O (5.70); found C (81.68), H (7.59), N (5.01), The above aldehyde 5 (0.2 g, 0.52 mmol) was condensed
O (5.73).
-hexyl-9H-carbazol-3-yl) methanol (3)
separately with cyano acetic acid (0.088 g, 1.04 mmol) and
rhodanine-3-acetic acid (0.198 g, 1.04 mmol) in acetonitrile in
presence catalytic amount of piperidine. The orange colored
solid was separated out, filtered and dried under vacuum and
the products were purified by silica gel column
chromatography using dichloromethane and methanol as
eluent [9:1 by vol.], to give orange powder SK2 (0.209 g, 72%)
and SK3(0.173 g, 74%).
9
The above product 2 (1.3 g, 4.6 mmol) was converted into
corresponding alcohol using sodium borohydride (0.176 g, 4.8
mmol) in THF at room temperature to give 9-hexyl-3-hydroxy
methyl carbazole. The product was extracted with
dichloromethane and purified by column chromatography on a
silica gel column using hexane and ethyl acetate as eluent [4:1
1
by vol.], (1.23 g, 94%). H NMR (400 MHz, CD
1
H NMR (400 MHz, CDCl ) SK2: δ 0.9 (t, J = 4.8 Hz, 3H), 1.32-
3
3
COCD
3
): δ = 0.8
1
.58 (m, 6H), 1.8-1.9 (m, 2H), 4.3 (d, J =7.2 Hz, 2H), 4.5-4.6 (s,
H), 7.18 (d, J = 17.2 Hz, 1H), 7.3 (d, J = 12.4 Hz, 1H), 7.35-7.45
(t, J = 7.2 Hz, 3H), 1.2-1.5 (m, 6H), 1.9 (t, J = 7.2 Hz, 2H), 4.1 (s,
2
1
H), 4.45 (t, J = 7.2 Hz, 2H), 4.8 (d, J = 4.0 Hz2H), 7.2 (m, 1H),
.4-7.65 (m, 4H), 8.15 (m, 2H). Elemental analysis calcd. for
(
m, 2H), 7.45-7.5 (m, 3H), 7.6-7.8 (m, 3H), 7.9-8.1 (m, 2H),
.15-8.25 (m, 1H), 8.35 (s, 1H). Elemental analysis calcd. for
(SK2): C (69.25), H (5.50), N (5.00), O (8.74), S
11.52) found C (69.28), H (5.46), N (5.04), O (8.62), S (11.56).
7
8
C
19
H23NO, C (81.11), H (8.23), N (4.99), O (5.68); found C
32 30 2 3 2
C H N O S
(81.09), H (8.25), N (4.97), O (5.69).
(
1
3
C NMR (DMSO δ / ppm):153.4, 118.0 , 152.9, 152.0, 62.2,
20.0, 40.14, 120.0, 128.6, 128.7, 128.7, 132.0, 132.0, 133.24,
18.3, 131.40, 131.50, 131.98, 118.3, 128.3 , 62.02, 153.4,
1.2, 51.7, 120.0, 39.52 , 39.10, 30.92, 26.09, 39.93, 21.9,
(
(9-hexyl-9H-carbazol-3-yl) methyl) triphenylphosphonium
1
1
5
1
bromide (4)
The synthesized compound 3 (1.2 g, 4.26 mmol) dissolved in
dichloromethane followed by addition of triphenyl phosphine
hydrobrimide (1.51g, 4.4 mmol) and reaction mass was stirred
at 40◦C for 18 h. After completion of reaction, solvent was
evaporated to dryness. Paste like mass was treated with
3.47.MS, m/z: calcd. for C32
+
55.46(M ).
H
30
N
2
O
3
S
2
: 554.72, found:
5
1
1
H NMR (400 MHz, DMSO),) SK3: δ H NMR (400 MHz, DMSO),)
SK3: δ 0.81 (t, J = 11.2 Hz, 3H), 1.3 (m, 6H), 1.65-1.78 (m, 2H),
excess diethyl ether to yield white colored solid powder (1.57
1
g, 75%). H NMR (400 MHz, CDCl
4
.36 (t, J = 4.8 Hz, 2H), 6.8 (s, 1H), 6.9 (d, J = 12.4 Hz, 1H), 7.35-
.7 (m, 2H), 7.30-7.65 (m, 4H), 7.81-8.46 (m, 6H). Elemental
3
): δ = 0.85 (t, J = 6.8Hz, 3H),
7
1
2
1
.3 (m, 4H), 1.8 (m, 4H), 4.2 (t, J = 7.6 Hz, 2H), 5.45 (d, 13.2 Hz,
analysis calcd. for C30
6.30), O (7.16); found C (80.32), H (6.28), N (6.24), O (7.12). C
NMR (DMSO δ / ppm): 162.5, 65.94, 128.66, 128.5, 39.92,
28 2 2
H N O (SK3): C (80.30), H (6.25), N
H), 7.05 (t, 7.2 Hz, 2H), 7.3-7.4 (dd, J = 1.6 Hz, 2H), 7.45 (t,
H), 7.6 (s, 1H), 7.65 (m, 6H), 7.75 (m, 10H). Elemental analysis
13
(
calcd. for C37
H37NBrP, C (73.23), H (6.18), N (2.30), P (5.11), Br
3
1
1
9.72, 120.06, 40.13, 131.90, 135.10, 132.01, 119.4, 130.30,
28.76, 128.6, 120.1, 117.05, 131.40, 151.86, 77.75, 77.37,
(13.18); found C (73.25), H (6.14), N (2.32), P (5.11), Br (13.17).
4-(2-(9-hexyl-9H-carbazol-3-yl)vinyl)benzaldehyde (5)
28.66, 39.30, 152.49, 86.32, 28.47, 26.09, 22.31, 22.20, 14.1.
+
447.95, found: 448.5(M )
MS, m/z: calcd. for C30
H
28
N
2
O
2
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